Process for modification of olefin polymers



mud

May 27. et. ass ras invendon relates to a process for modification of polymeric compositions and in a more particular sense it relates to such a process which is especially applicable to aliphatic polymers. Still more particularly the process this invention involves the incorporation nto aliohatic ZJQrjlliil'S of phosplorus, sulfur and chlorine.

'l. e tr atment turmoil u ng reagents has long been irnewu and been utilized widely for many diflereut The treat ment is exemplified by the reaction of a low molecular weight polymer of a low boiling olefin with phosphorus pentasulide. This reaction apparently involves the olefinic portion of the polymer molecule, although it does not appear to be definitely established whether or not the reactiott takes place at the olefinic double bond itself or at the carbon atom alpha to this double bond. in any event the principal result of such a reaction is the incorporatio or losphorus and sulfur into the polymeric chain and this product is susceptible of various further reactions leading to many useful products. Many variations of this specific example are renown. Glelinic polymers of a wide molecular weights have been investigated in this process. lvlany phosphorus sulfides have been exploited, although phosphorus pentasulfide appears to have found widest usage. The reaction has been extended to copolyand such copolyrners have included those prepared from styrenes and substituted styreues. The use of phsphorus peutasulfidc iointly with elemental sulfur has been investigated and vfound to be useful for certain purposes.

subsequent treatment of these phosphorus and sulcouiaitnug polymers with steam, basic neutralization investigation.

established in some instances.

The utility of the compositions which have re sulted from the reaction of aliphatic polymers with phosyhonisand sulfur-containing reagents has indicated the value of this type reaction. Such products have been found to be useful chiefly as additives for use in mineral lubricants. The value of such products in other applications, likewise, has been well established. in almost all of such applications, including use in mineral lubricants, the value of the products has resided in the metal salts from these acidic products. Such metal salts in turn appear to have been useful in direct proportion to the stoichiometric amount of metal in the oil-soluble salt. Recent developments in the preparation of such metal salts, i.e., those which contain stoichiometrically excessive amounts of metal, have enabled the preparation or such metal salts which contain unusually large amounts of oral, and as indicated before the value of these metal salts is in direct proportion to the stoichiornetric amount of metal in the salt.

A principal object of the present invention is the provision of a process for the preparation of novel phosphorusarid sulfur-containing derivatives of olefin polymers.

Another object of the present invention is the provision of such a process by means of which products may be prepared which have an increased acidity over that of products prepared by previously-known processes.

Other objects of the invention will be apparent from the ensuing description thereof.

These objects are attained by the process of preparing our i ice iiatented Feb. 6, 1962i phosphorus, sulfur and chlorine-containing composi tions which comprises adding phosphorus trichloride to a. mixture of sulfur and an aliphatic olefin polymer at a temperature above 149 C., the mole ratio or the total amount of sulfur used to the total amount of phosphorus trichloride used being at least 1:1. The product which results from this process contains reactive chlorine and as such is susceptible to further modification with water, alcohols, phenols and basic reagents. The products which result from such modification steps are acids, esters or salts.

The olefin polymers of the above process are those derived principally from aliphatic mono-olefins. Such polymers may include minor amounts of other c0-rnonomer units such as di-oleiins or aliphatic vinyl monomers. The olefins from which the polymers of this process are prepared are for the most part the low molecular weight olefins including chiefly ethylene, propylene and isobutylene. The reason for this rests not only with the commercial availability of these particular olefins and the polymers derivable therefrom, but also because of their particular utility in the process and the elfectiveness of the products which result from their use in the process.

in addition to polymers of olefins, other aliphatic vinyl polymers likewise may be employed in the process. Such vinyl polymers include for example polyvinyl acetate, polyvinyl chloride, polyvinyl others, and acrylates.

In general the lower molecular weight polymers of these olciins are more satisfactory than the higher molecular weight polymers. The term lower molecular weight is intended to mean a range of from 250 to 3000. Higher molecular weight polymers. are useful in certain instances and the use of such higher molecular weight polymers is contemplated as being within the scope of this invention. in most cases, however, the use of such higher molecular weight polymers is less convenient for reasons of solubility and viscosity, not only in the process mixture but in subsequent uses of the product which results.

The use of copolymcrs in the process, likewise, is within the scope of the invention to the extent that such copolyruers must be aliphatic. Thus such copolyrners which contain minor proportions of vinyl acetate or vinyl chloride, or butadiene can be used in the process and the products which result are useful in certain applications.

The preparation or" the olefin polymers which comprise the starting material of the process of this invention may be effected according to any of various well-known polymerization techniques. A particularly useful method comprises the treatment of an olefin such as isobutylene at temperature from about -6() C. to about 46 C. in the presence of a catalyst such as boron fluoride. The preparation of the particularly suitable low molecular weight polymers for this process may be carried out as follows: A hydrocarbon mixture containing about 25% of isobutylcuc is cooled to about -l5 C. and from 0.1% to about 2% of boron fluoride, based upon the isobutylcne content of the material treated, is added with vigorous agitation. The exothermic nature of the poly merization requires efiicient cooling. When the polymerization has subsided the reaction mass is neutralized and washed free of acidic substances arising from the catalyst. The resulting polymer is separated from the unreacted hydrocarbons by distillation. The residual polymer so obtained, depending upon the temperature of reaction, contains polymeric chains having molecular weights within the range of to 2000.

Higher molecular weight olefin polymer may be obtained by other well-known methods, viz., low temperature polymerization with boron fluoride catalyst, or high pressure, high temperature conditions with a freeq'adical type of catalyst. Other catalysts may be used, particularly in the preparation of the lower molecular weight is in unusuaiiy the product I witita She;

.oacizion i- 1 N OM pozymyr -3i1 rus K123193166 1/940 v Hilffliififfi. fine z'easnoo r:

3 hour 0 amps) d, 1 a 1 3 i .W following product o the addition ohosahorm more ea s of the above products is substantiail" i' e' W 3 which ticai with ih product obtainad by a process pho nhorus irichioride and sulfur @2012 a! poriion' T 2 01mm polymer.

As noted previousiy the minimum tomperature room for the successful operation of the hcrcindescribeci pro process iakes place only to a negligible e may be carried out is resiricted only by t e voiaiiiii gi'hosphorus 'iricifioride and 'Zhe pain 3,6 x3l3,58'3l {80% of ills:Ethommlicalylolcl) iriclilo'. surflaoo oi reaction mass llzroughmzt 9 Near the and of the 1 was added to the mil:- in: to C. To 1645 all-owe oil sollsilozs, 208 grams added a: 35 '1; xide oclahy was, at jifiklx for 4 hours flislillatioml Benzene was then reare o 120 (1/12 mm. The grams and 'klze following ie weighed 116?. grams Jwas found to haw: theiollowi g,

l (1&2 moles) of sulfur, and To this mi:- 1

moles) i and tho l, mums of mineral oil. This oil of 2's: *haoretical 5,-

f l Trace l, was mood lfilllyi i'flfi having an lllero was added of sulfur in 2 first porlioa: 1 '8 grams {4.38 lzloricls throughout a "period of Tlwmafter ll'ie :eaclion mixture was heatsd esi rs and than al 125 G/mm. "Elm i 53% of tho theoretical.

H 1 portions, Example why? :57 (4.9 polyisoom n m ,r cow was mole} like above l. lllkku I lvj heated to 12$ s. The residue wolglxe 345 grams oc yield) and had the following .mwnuuwmn-nwnfluu. 2.99 3.59- 9.0:;

Example mixiuyg was To lO'OO grams (0.95 mole) of 21 dlocarbon polylnes Th ixt th n wgg. having a .Trolecular waighl of about 3009-1100 (preparad by 3301 1;: aiion of a mixturs of olelmic monomers liav ing =4 molaculal" V /sight approximating 90 and comyxosad cssezzllzzl of (ii-ones and reactive olefins) chore was (led at 18f. C. 43 (1.33 moles) of suliuy an small s lions and Oll:3\1llg tho addition. of the first portion of sulfur more was added in small portions 185 grams {1.33 moles) phosphorus H loride. Th2 n'iixturs was healed a2 22% E. for how: and than at 200 {H mm. The residue was cllluled wiih 1000 T9 6 lliixilll'fi Of 3233' g s TR35} 05 m3 @709? grams maze-rial oil andilie *sluiion, weighing 2078 PYCUULL, 145C of mineral ml Wu grams 3%: grams Q5757 am. m yifim); was fgmd to Water, there was slowly added at 30 (3., 2% grams (1.3 11mm ,gmqowim an gym? U MW ,l l molas) of oanum oxxcla. lhc macuon mass was heated Q "'3 to -l00 C to complete lhe rsactlon and men dried at gleam l {-2 1513-460 0/30 mm. The residue than was filtarccl. The Pwmt 5 3 fi 'iralc, Weighing 269l grams (93% of the ll'zcorelical Pawn C1 7 c 1 N lmo val, lound lo have the followulg analyses. 65 mph 53 Sodium Zmthylhcxyl alcoholale was prepared by adding ll grams (0.47 mole) of sodium to 600 ml, of fZ-etbyillexyl alcohol at C. "[0 Hill; mixiuro there was added 70 a solution of 243 grams (0.33 mole) of a phosphorus-, v Example 6 sulfur-, and chlorinecontaining compound prepared ac- TO a mixture of 1700 grams (23 moles) of poll/55ocording to Example 1 in 500 ml. of benzene. The mixlmiyleno having an average molecular weight of 700 800 lure refluxed 61 C. for 8 Washed with and 326 grams (10.2 moles) of sulfur, there wa added, Wlilel, and the organic portion heated to 0/5 mm. at 148-150 C. 480 grams (3.5 moles) oi phosphorus g5 to remove all volatile substances such as water, benzene a resiciua wsi fer 6.5 3mm, The rssidma waa diluted Wifiii 2480 grams of and aicahei, '11, 192 grams and had fellowing miaiyses mineral oil, and the ofl. soluu'an was inland to haw: the

mixma'ai of gxms (1.9 mobs) of thevabove produ and g'z'ams 13. f1 03%) a poiyisobutyl phimcl {@bmm ph-emi with an aquimolar J37 aikyia zon 0i amsunt of a 3 oiyisobut' lane having an averaga moiecular weight a 397-350 in 231v pa'essme. of sulfuyic as T he 36 a 248-265 C. for residue Weighed zmd had he mixture:

a I grama (6.6

3 molecular 309 61 $42 2 c. a

kamuwunm Q Mm. 1.3 muma-.,m,-..mm".(mmmmuwmu.B.n.Mm... 1.1 2;; 1 53-35311, 3 V Mum if u MM, @144 -WWWWWWMmmw--mmmmflmma; m, WOW.-wm.m-Mwnuwm -m- Sa Nenkmwm.WWMMWMWMMW 4 X ks) golyisoou'iylem iizzikg To 867 grams (9.33 mafia a? wig/ethylene z'ggwv 700-66? we :zwiacular waight of 2509-2749 than? was added a! l p-1A 4:201 035 Fsolesy or ulfur 170 C. 158 grams (5.75 1210166) 075 sulfur in 51212131 ag-mans, am. rollowmg ma addmsn 0x me mat pmtmn 0f psmons, and foiiowing the addition of Ehffi firs JECU'G i iimr a was added 1148 (8.35 mmlas} of of sulfur, there was 2.5526. graduafily 485 *rama gmosphm'us alyichinride small gortians ociow ine surmoles) m? phosphorus iriciaieride ihroughcui a named 0'; face of a raactmn mass. Tim mixture was Leatc, 12 hears, The mixiux's was eafised to 169 -370" C. and we! Artur m .iarZheum and mm at 206%10" CIJ/BO '75 dihateci xvi-1h 43G graas 0i mileml 0i The 5611211021 5; coiimoerabie evoluiiori Stirr r was continued over a en so i lieres. tiara meie} a geoigriso butylene Weivii: of 10,039 4-5 gran u 13.3 gra heated hours and i142 held an 208411? hours. lne reaction mixture i3. 20 mm. Tue *esidue was o mineral oil a Mia Brim? was blown through 593 grams of t le above piocl butyieue "M. A 5 5 0d am am cl o -alicliioie enzene was heated at 3.79

moles} of was adclezi poi- (i.i25 moles} of phos'r adciitioo of these we reactants of four hours. The tempera lieu-es and thee 8% grams -33. Wiiiii: 45 grams (l tionwise, aml them reopen will oi' disiiliaie was was ciiluied with 1,000 grams u z'esulting solution ii'eated wiio The i-csidue was it iii/ 370 This dried, mate tied o3 henamg i) IL/3C lia the following 0.6

ated at 380 (1 I: of elzospliozus amides thereof, are i insecticides, etc.

0E ihe phospiiorus 5 compounds may oeused, We ag is aspheli emulsions; as i in lubi'icanzs; as light and heat staelastic compositions; as insecticides, as paints; etc. The 6Sti5 and 2111-: i: ides of the phosphorus-, i, i 3? anti $l'1lGllfi-BOli2-.l g compounds may, for exbe used metal'ree dispez'sants or detergents in micizers; etc. In ihese s invention may be emeomctimes from aboui often from about 6.05%,

the Weight of the total composifor example (ilSjBEBX'SEXEi 'zers p 9.91% to aboul 20%, and mo to about 5% cm i101": Jilim employed wi i the foregoing specified e i' ii'ooucis of ihis inveu lien an; usually in the compositions. mince small percentages of the pioducts of this im'eniion in. ihe various applications ofzeu importance chat the addition agents be compleiely soluble in all proportions. Also, certain comgiounds are of value as gelling or bodying agcms when used in amounts greater lhan are strictly soluble. In incorporating the products of this invention into the various end compositions, which may be in the form of a homo gencous soluizioo, a dispersion, a suspension, or an emulsion, there is usually little difficulty encountered, especially if the incorporation is eilectecl Wlil'l the assist ance of mechanical dispersing means such as vigorous agitation ox ultrasonic radiation.

3pecific examples illustrating a few of the various 

1. THE PROCESS OF PREPARING PHOSPHORUS-, SULFUR-, AND HALOGEN-CONTAINING COMPOSITIONS WHICH COMPRISES PREPARING A MIXTURE OF PHOSPHORUS TRIHALIDE, SULFUR AND AN ALIPHATIC POLYMER, AND HEATING SAID MIXTURE AT A TEMPERATURE ABOVE 140* C. BUT BELOW THE DECOMPOSITION POINT OF THE COMPONENTS OF THE REACTION MIXUTRE, THE MOLE RATIO OF THE TOTAL AMOUNT OF SULFUR USED TO THE TOTAL AMOUNT OF PHOSPHORUS TRIHALIDE USED BEING AT LEAST 1:1 AND THE MOLE RATIO OF THE TOTAL BEING AT PHOSPHORUS TRIHALIDE USED TO THE TOTAL AMOUNT OF ALIPHATIC POLYMER USED BEING AT LEAST 1:1. 